Polymer

ABSTRACT

The present application relates to a polymer and a use thereof. The present application may provide a functional polymer which expresses a low solubility to a polar solvent and a non-polar solvent and which is suitable for forming a film. If applied to the use of cosmetics such as mascara or to medical uses, the polymer in the present application may express a tolerance to diverse solvents such as sebum, sweat, tears and the like, and thus enables makeup to last, etc. Accordingly, the polymer may be applied to diverse uses and used in film forming agents, cosmetic compositions, or cosmetics, or the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a national entry under 35 U.S.C § 371International Application No. PCT/KR2015/013741 filed Dec. 15,2015,which claims priority to Korean Patent Application No. 2014-0180724filed on Dec. 15, 2014, the disclosure of which is herein incorporatedby reference.

TECHNICAL FIELD

The present application claims the benefit of priority based on KoreanPatent Application No. 2014-0180724 filed on Dec. 15, 2014, thedisclosure of which is herein incorporated by reference in its entirety.

The present application relates to a polymer, a film forming agent, acosmetic composition and a cosmetic, comprising the polymer.

BACKGROUND ART

Polymers having resistance to oil-based and water-based solvents andsuitable for forming a film have been variously required. For example,in cosmetics such as mascara, or cosmetics or drugs that are applied toother skins, polymers having resistance to solvents of differentproperties such as sweat, tears and sebum and capable of forming a filmmay be required. Polymers, which are applied in preparing cosmetics, aredescribed in Patent Documents 1 and 2.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Unexamined Patent Publication No.2000-119140

Patent Document 2: Japanese Unexamined Patent Publication No.2003-055136

DISCLOSURE Technical Problem

The present application provides a polymer, and a film forming agentcomprising the polymer. It is one main object of the present applicationto provide a functional polymer, suitable for forming a film, which mayexhibit low solubility in polar and non-polar solvents prevent fromblurring against the solvents, and a use thereof.

Technical Solution

The polymer of the present application comprises polymerized units of ahydrophilic monomer, polymerized units of a hydrophobic monomer andpolymerized units of a compound comprising silicon atoms.

By appropriately comprising the above monomers, it is possible to form apolymer, suitable for forming a film, which may prevent from blurring invarious conditions, with exhibiting low solubility in polar andnon-polar solvents.

Such a polymer of the present application may be applied to cosmetics,such as mascara, or articles to be used in human bodies, such as medicalsupplies, to have resistance to sweat and sebum and the like and toexhibit a film forming ability suitable to the above applications.

In the present application, the polymerized unit of any monomer orcompound means a form in which the monomer or compound is included inthe polymer as a monomer unit via a polymerization reaction.

For example, the polymer may comprise as the hydrophobic monomer a firstmonomer of which homopolymer has a solubility parameter of less than10.0 (cal/cm³)^(1/2).

In the present application the solubility parameter refers to asolubility parameter of a homopolymer prepared by polymerizing thecorresponding monomer, through which the degree of hydrophilicity andhydrophobicity in the corresponding monomer may be found out. A methodof obtaining the solubility parameter is not particularly limited, andmay be in accordance with a method known in the art. For example, theparameter may be calculated or obtained according to the method known inthe art as the so-called HSP (Hansen solubility parameter). Here, inanother example, the solubility parameter of the homopolymer of thefirst monomer may be in a range of 5 (cal/cm³)^(1/2) to 9.5(cal/cm³)^(1/2) or 7 (cal/cm³)^(1/2) to 9 (cal/cm³)^(1/2).

As the first monomer, as long as it has the above solubility parameter,various types of monomers may be selected and used. The monomer usableas the first monomer may be exemplified by alkyl (meth)acrylate oraromatic (meth)acrylate.

An alkyl group included in the alkyl (meth)acrylate may be exemplifiedby a straight, branched or cyclic alkyl group having 1 to 20 carbonatoms, 4 to 20 carbon atoms, 8 to 20 carbon atoms or 10 to 20 carbonatoms and the alkyl group may be optionally substituted by one moresubstituents. In the present application the term (meth)acrylate maymean acrylate or methacrylate. Such a monomer may be exemplified bymethyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl(meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate,2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl(meth)acrylate, isobutyl isobornyl (meth)acrylate, isooctyl(meth)acrylate, isononyl (meth)acrylate or lauryl (meth)acrylate, or thelike, without being limited thereto.

The aromatic (meth)acrylate may be exemplified by aryl (meth)acrylate orarylalkyl (meth)acrylate. Here, an aryl group of aryl or arylalkyl maybe, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18carbon atoms or 6 to 12 carbon atoms. In addition, an alkyl group of thearylalkyl may be, for example, an alkyl group having 1 to 20 carbonatoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atomsor 1 to 4 carbon atoms. Here, the alkyl group may be straight, branchedor cyclic, and the alkyl group or the aryl group may be optionallysubstituted by one or more substituents.

The aryl group or arylalkyl group can be exemplified by a phenyl group,a phenylethyl group, a phenylpropyl group or a naphthyl group, but isnot limited thereto.

As the first monomer, for example, a compound represented by Formula 1below may be used.

In Formula 1 Q is hydrogen or an alkyl group, and B is a straight orbranched alkyl group having 5 or more carbon atoms or a alicyclichydrocarbon group, or an aromatic substituent such as the aryl group orthe arylalkyl group.

In Formula 1, as the alkyl group present in Q, an alkyl group having 1to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8carbon atoms or 1 to 4 carbon atoms may be used. The alkyl group may bestraight, branched or cyclic. In addition, the alkyl group may beoptionally substituted with one or more substituents.

In Formula 1, B may be a straight or branched alkyl group having 5 ormore carbon atoms, 7 or more carbon atoms or 9 or more carbon atoms,which may be optionally substituted or an unsubstituted state. Such acompound comprising the relatively long-chain alkyl group is known as ahydrophobic compound. The upper limit of the number of carbon atoms inthe straight or branched alkyl group is not particularly limited, andfor example, the alkyl group may be an alkyl group having up to 20carbon atoms.

In another example, B in Formula 1 may be an alicyclic hydrocarbongroup, for example, an alicyclic hydrocarbon group having 3 to 20 carbonatoms, 3 to 16 carbon atoms or 6 to 12 carbon atoms, and an example ofsuch a hydrocarbon group may be exemplified by an alicyclic alkyl group,and the like, having 3 to 20 carbon atoms, 3 to 16 carbon atoms or 6 to12 carbon atoms such as a cyclohexyl group or an isobornyl group. Such acompound comprising the alicyclic hydrocarbon group is also known as arelatively hydrophobic compound.

In the present application, the substituent, which may be optionallysubstituted on an alkyl group, an alkylene group, an aromaticsubstituent, an aryl group or a hydrocarbon group in Formula 1 above, orother Formulas to be described below, may be exemplified by halogen suchas chlorine or fluorine, a glycidyl group, an epoxy group such as anepoxyalkyl group, a glycidoxypropyl group or an alicyclic epoxy group,an acryloyl group, a methacryloyl group, an isocyanate group, a thiolgroup, an alkyl group, an alkenyl group, an alkynyl group or an arylgroup, and the like, but is not limited thereto.

In the present application an appropriate type may be selected from theabove monomers in consideration of the physical properties of thedesired polymer and used.

The polymer of the present application may comprise polymerized units ofa second monomer of which homopolymer has a solubility parameter of 10.0(cal/cm³)^(1/2) or more as the hydrophilic monomer. In another examplethe solubility parameter of the second monomer may be in a range of 10(cal/cm³)^(1/2) to 15 (cal/cm³)^(1/2) or 10 (cal/cm³)^(1/2) to 13(cal/cm³)^(1/2).

As the second monomer, it is possible to use a monomer selected frommonomers known to have the above solubility parameter.

For example, as the second monomer, a compound represented by Formula 2or 3 below may be used.

In Formula 2, Q is hydrogen or an alkyl group, U is an alkylene group, Zis hydrogen or an alkyl group, and m is any number:

In Formula 3, Q is hydrogen or an alkyl group, A and U are eachindependently an alkylene group, and X is a hydroxy group or a cyanogroup.

In Formulas 2 and 3, as the alkyl group present in Q and Z, an alkylgroup having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbonatoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms may be used. The alkylgroup may be straight, branched or cyclic. In addition, the alkyl groupmay be optionally substituted with one or more substituents.

In Formulas 2 and 3, m and n may be any number, and for example, eachindependently a number in a range of 1 to 100, 1 to 90, 1 to 80, 1 to70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 16 or 1 to 12.

In one example, as the second monomer, a compound, wherein in Formula 2above Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U isan alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkylgroup having 1 to 4 carbon atoms, and m is 1 to 20, may be used, but isnot limited thereto.

The polymer may comprise 50 to 99.9 parts by weight of the polymerizedunits of the first monomer and 0.1 to 20 parts by weight of thepolymerized units of the second monomer. Here, in another example, thepolymerized units of the first monomer may exist in 60 to 99.9 parts byweight, 70 to 99.9 parts by weight or 80 to 99.9 parts by weight. Inaddition, the polymerized units of the second monomer may be containedin 5 to 20 parts by weight or 7 to 20 parts by weight. In the presentapplication, the unit part by weight may mean a ratio of weight betweenthe respective components, unless otherwise specified. Furthermore, theweight ratio of the polymerized units of the monomer may mean the weightratio of the monomer applied on preparing the polymer. Thus, forexample, the phrase the polymer comprises 50 to 99.9 parts by weight ofpolymerized units of the first monomer and 0.1 to 20 parts by weight ofpolymerized units of the second polymer may mean that the polymer hasbeen formed by polymerizing the monomer mixture comprising the firstmonomer and the second monomer in a weight ratio of 50˜99.9:0.1˜20(first monomer:second monomer). If the weight ratio of the secondmonomer in the polymer is less than 0.1 parts by weight or the weightratio of the first monomer is more than 99.9 parts by weight, theresistance to the oil-based solvent or the sebum proofness may not beenough, and if the weight ratio of the second monomer exceeds 20 partsby weight or the weight ratio of the first monomer is less than 50 partsby weight, the polymer cannot be formed by the phase separation, or theresistance to the polar solvent or the resistance to sweat or tears maynot be enough.

In another example, the polymer may comprise at least 50%, at least 55%,at least 60%, at least 65%, at least 70%, at least 75% or at least 80%,of polymerized units of the first monomer, based on weight. The ratio ofpolymerized units of the first monomer may be 99% or less, 98% or less,97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% orless, 91% or less, or 90% or less, based on weight. In the above state,the polymer may comprise the polymerized units of the second monomer ina ratio of 40 parts by weight or less, 35 parts by weight or less, 30parts by weight or less, 25 parts by weight or less, 20 parts by weightor less, 15 parts by weight or less, 10 parts by weight or less or about8 parts by weight or less relative to 100 parts by weight of thepolymerized units of the first monomer. The polymerized units of thesecond monomer may be contained in a ratio of at least about 0.1 partsby weight, at least 0.15 parts by weight, at least 0.2 parts by weightor at least 5 parts by weight ratio relative to 100 parts by weight ofthe polymerized units of the first monomer. While the resistance to theoil-based solvent or the sebum proofness is secured in the above ratio,the resistance to the polar solvent, or the resistance to sweat or tearsor the like can be also effectively secured.

The polymer may also comprise additional monomers in addition to theabove-described first and second monomers.

For example, the polymer may comprise a compound comprising a siliconatom, for example, a compound of Formula 5 below as polymerized units.The compound of Formula 5 below may perform functions to maintain abalance of water resistance and oil resistance within the polymer andfurther increase glossiness.

In Formula 5, R₁ to R₆ are each independently hydrogen, a hydroxy group,an alkyl group, an alkoxy group, an alkenyl group, a (meth)acryloylgroup, a (meth)acryloylalkyl group, a (meth)acryloyloxy group or a(meth)acryloyloxyalkyl group, provided that at least one is an alkenylgroup, a (meth)acryloyl group, a (meth)acryloylalkyl group, a(meth)acryloyloxy group or a (meth)acryloyloxyalkyl group.

In addition, in Formula 5, n is a number in a range of 0 to 20 or 0 to15. In Formula 5, n can be 0 or a number in the range of 1 to 20 or 1 to15.

In Formula 5, the alkyl group or alkoxy group may be exemplified by astraight, branched or cyclic alkyl group or alkoxy group having 1 to 20carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbonatoms or 1 to 4 carbon atoms, which may be optionally substituted by oneor more substituents.

In Formula 5, the alkenyl group may be exemplified by a straight,branched or cyclic alkenyl group having 2 to 20 carbon atoms, 2 to 16carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbonatoms, which may be optionally substituted by one or more substituents.

In Formula 5, at least one of R₁ to R₆ is a polymerizable functionalgroup such as an alkenyl group, a (meth)acryloyl group, a(meth)acryloylalkyl group, a (meth)acryloyloxy group or a(meth)acryloyloxyalkyl group, by which the compound may be contained inthe polymer as polymerized units. In general, the polymerizablefunctional group may be a (meth)acryloylalkyl group or a(meth)acryloyloxyalkyl group, where the alkyl group may be a substitutedor unsubstituted, straight, branched or cyclic alkyl group having 1 to20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8carbon atoms or 1 to 4 carbon atoms as described above.

In Formula 5, at least one, two or more or three or more of R₁ to R₆ maybe an alkoxy group.

In one example, the compound of Formula 5 may be a compound in which inFormula 5 above, n is 0 and R₁, R₃, R₅ and R₆ are each independentlyhydrogen, an alkyl group, an alkoxy group, a (meth)acryloylalkyl groupor a (meth)acryloyloxyalkyl group, provided that at least one, two ormore or three or more of R₁, R₃, R₅ and R₆ are an alkoxy group and atleast one of R₁, R₃, R₅ and R₆ is a (meth)acryloylalkyl group or a(meth)acryloyloxyalkyl group. In this case, the alkyl group may be analkyl group having 1 to 8 carbon atoms and the alkoxy group may be analkoxy group having 1 to 8 carbon atoms.

In another example, the compound of Formula 5 may be a compound in whichin Formula 5 above, n is a number in the range of 1 or more, 1 to 20 or1 to 15 and R₁ to R₆ are each independently hydrogen, an alkyl group, analkoxy group, a (meth)acryloylalkyl group or a (meth)acryloyloxyalkylgroup, provided that at least one of R₁ to R₆ is a (meth)aryloylalkylgroup or a (meth)acryloyloxyalkyl group. In this case, among R₁ to R₆ afunctional group other than the (meth)acryloylalkyl group or(meth)acryloyloxyalkyl group may be an alkyl group. Here, the alkylgroup may be an alkyl group having 1 to 8 carbon atoms and the alkoxygroup may be an alkoxy group having 1 to 8 carbon atoms.

The polymer may comprise 50 to 99.9 parts by weight of polymerized unitsof the first monomer, 0.1 to 20 parts by weight of polymerized units ofthe second monomer and 0.1 to 10 parts by weight of polymerized units ofthe compound of Formula 5 above. Here, when the ratio of the polymerizedunits of the compound of Formula 5 is too low, the effect due toaddition of the compound, for example, the effect of impartingglossiness to a film or preventing blurring, may be minimal, and when itis too high, the polymer may exhibit the physical properties that arenot suitable for forming a film.

In another example, the polymer may comprise at least 50%, at least 55%,at least 60%, at least 65%, at least 70%, at least 75% or at least 80%,of polymerized units of the first monomer, based on weight. The ratio ofthe polymerized units of the first monomer may be 99% or less, 98% orless, 97% or less, 96% or less, 95% or less, 94% or less, 93% or less,92% or less, 91% or less, or 90% or less, based on weight. In the abovestate, the polymer may comprise polymerized units of the compound ofFormula 5 above in a ratio of 20 parts by weight or less, 15 parts byweight or less, 13 parts by weight or less, 10 parts by weight or lessor about 8 parts by weight relative to 100 parts by weight of thepolymerized units of the first monomer. The polymerized units of thecompound of Formula 5 above may be contained in a ratio of about 0.1part by weight or more, 0.15 parts by weight or more, 0.2 parts byweight or more, about 0.5 parts by weight or more or about 1 part byweight or more relative to 100 parts by weight of the polymerized unitsof the first monomer. While the resistance to the oil-based solvent orthe sebum proofness is secured in the above ratio, the resistance to thepolar solvent, or the resistance to sweat or tears or the like can bealso effectively secured.

The polymer can be produced by a known polymerization method using thefirst and second monomers and a silicon atom-containing compound andother necessary monomers. In one example the polymer may be prepared bya solution polymerization method using a solvent, for example, anorganic solvent, for example a radical solution polymerization method.For example, when the polymer is applied to an application in contactwith a human body such as cosmetics, as a solvent in the polymerizationprocess, a solvent friendly to the human body can be selected and used.Such a solvent may be exemplified by isododecane, isoparaffin orisohexadecane, and the like, but is not limited thereto.

In the present application, the polymer may have a weight averagemolecular weight (Mw) in a range of 10,000 to 500,000. In the presentapplication, the weight average molecular weight may be, for example, aconverted value of the standard polystyrene measured using GPC (GelPermeation Chromatograph), and the term molecular weight can refer tothe weight average molecular weight, unless otherwise specified. Forexample, when the polymer is applied as a film forming agent, the abovemolecular weight (Mw) may be useful. By using the polymer in the abovemolecular weight (Mw) range, it is possible to form a film efficientlywithout an agglomeration phenomenon and the like.

In addition, the polymer may have a glass transition temperature of 10°C. or more. In another example, the glass transition temperature may be15° C. or more, 20° C. or more, 25° C. or more, or 30° C. or more. Theglass transition temperature of the polymer may be about 110° C. orless, about 100° C. or less, 90° C. or less, 80° C. or less, 70° C., 60°C. or less, or 55° C. or less. In the present application, the glasstransition temperature is a theoretical value obtained through theso-called Fox equation from the monomer composition of the polymer. Whenthe polymer is applied as a film forming agent, the above glasstransition temperature may be useful. By using the polymer in the aboveglass transition temperature range, it is possible to form a filmefficiently without a stickiness or brittleness phenomenon and the like.

The polymer of the present application may exhibit a low solubility inboth polar solvents and non-polar solvents. In the present application,the term non-polar solvent may mean a solvent having a dielectricconstant at 25° C. in a range of about 1 to about 3, about 1.5 to 2.5 orabout 1.5 to 2 or so, and the term polar solvent may mean a solventhaving a dielectric constant at 25° C. in a range of about 75 to about85 or about 75 to 80. A representative example of the non-polar solventmay include hexane (dielectric constant (25° C.): about 1.89), and arepresentative example of the polar solvent may include water(dielectric constant (25° C.): about 78.54), without being limitedthereto. In chemistry, the dielectric constant for the solvent is wellknown for each solvent.

In one example the polymer may have solubility in the polar solvent of10 or less, or 5 or less. The polymer may have solubility in thenon-polar solvent of 10 or less, or 5 or less. It means that the lowerthe value of the solubility, the polymer has more excellent resistanceagainst the polar and non-polar solvents, so that the lower limit is notparticularly limited. For example, the solubility in the polar solventand the non-polar solvent may be about 0.001 or more, about 0.01 ormore, about 0.1 or more, or about 1 or more, respectively. In thepresent application, solubility in a specific solvent refers to grams(g) of a polymer that can be dissolved in 100 g of the correspondingsolvent as much as possible. Furthermore, unless otherwise specified,the solubility in the present application refers to solubility measuredat room temperature. The term room temperature is a natural temperaturewithout warming or cooling, and for example, may be a temperature in arange of about 10° C. to 30° C., about 15° C. to 30° C., or about 20° C.to 30° C., or a temperature of about 25° C. or so. In the case of thecharacteristic, the value of which varies depending on temperatures,such as the solubility, among characteristics mentioned in thisspecification, the corresponding characteristic is a characteristic atroom temperature, unless otherwise specified.

The polymer can exhibit a suitable solubility in the intermediate stepsolvents between the polar and non-polar solvents. For example, thepolymer may have solubility in a range of 20 or more or about 20 to 50in the solvent having a dielectric constant at 25° C. in a range of 4 to15, 5 to 15, 5 to 10, 5 to 8 or 5 to 6.5. Such a solvent may beexemplified by ethyl acetate (dielectric constant (25° C.): about 6.02)and the like, without being limited thereto.

The present application also relates to a film forming agent, a cosmeticcomposition or a cosmetic, comprising the polymer. If theabove-described polymer is used, it is possible to form a uniform film(coating) by application, to exhibit high stability even when applied toskin, and to show excellent resistance to various solvents such assweat, tears or sebum by exhibiting a resistance to both polar andnon-polar solvents.

Accordingly, the polymer can be applied to prepare a film forming agentor a cosmetic composition capable of being used in producing variouscosmetics, including, cosmetic packs, make-ups, such as mascara, appliedto lips or eyes, nail polishes which can be applied to fingernails ortoenails, lipsticks, eye shadows, hair styling products or eyeliners,etc. In addition, the polymer or the film forming agent or the like mayalso be applied to a medicinal use, and the medicinal use may beexemplified by bandages or transdermal absorption formulations and thelike.

The ratio of the polymer in the film forming agent, the cosmeticcomposition or the cosmetic is not particularly limited, which may beselected in consideration of application purpose. For example, if thepolymer is applied to the cosmetic composition, the concentration of thepolymer in the composition may be in the range of 1% by weight to 20% byweight, but is not limited thereto.

The film forming agent, the cosmetic composition or the cosmetic mayfurther comprise other active ingredients depending on applications.Additional active ingredients may also be exemplified by medicinalingredients, physiologically active ingredients or pharmacologicallyactive ingredients as well as cosmetic ingredients such as whitening orsunscreen. Such an active ingredient may be exemplified by topicalanesthetic ingredients (lidocaine, dibucaine hydrochloride, dibucaine,ethyl aminobenzoate, etc.), analgesic ingredients (salicylic acidderivatives such as methyl salicylate, indomethacin, piroxicam,ketoprofen, felbinac, etc.), anti-inflammatory ingredients(glycyrrhizinic acid, salts glycyrrhizinate such as dipotassiumglycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinate,bufexamac, benzyl nicotinate, hydrocortisone, hydrocortisone butyrate,hydrocortisone acetate, prednisone valeroacetate, prednisone acetate,prednisone, dexamethasone, dexamethasone acetate, dimethyl isopropylazulene ibuprofenpiconol, arnika extract, Scutellaria Baicalensis Rootextract, cattail ear extract, chamomile extract, calamine, licoriceextract, guaiazulene, gardenia extract, gentiana extract, black teaextract, tocopherol, tocopheryl acetate, lithospermum extract, perillaextract, peony extract, sage extract, Swertia japonica extract, MulberryRoot extract, pyridoxine hydrochloride, peach leaf extract, cornflowerextract, saxifrage extract, mugwort extract, roman chamomile extract,etc.), anti-histamine ingredients (chlorpheniramine maleate,diphenhydramine, diphenhydramine hydrochloride, diphenhydraminesalicylate, ISO pen zyl hydrochloride, etc.), local irritationingredients (ammonia, 1-menthol, dl-can full, peppermint oil, nicotinicacid, benzyl niconinate, nonylic acid vanilylamide, etc.), antipruriticingredients (crotamiton etc.), preservative or sterilizing ingredients(acrinol, chlorhexidine gluconate, chlorhexidine hydrochloride,benzalkonium chloride, benzethonium chloride, povidone iodine, iodoform,iodine, potassium iodide, merbromin, oxides, cresol, triclosan, phenol,isopropyl methyl phenol, thymol, sodium salicylate, undecylenic acid,photosensitizer, hinokitiol, phenoxyethanol, chlorobutanol, quaternium73, zinc pyrithione, para-hydroxybenzoic acid esters, eucalyptusextract, resorcin rosemary extract, etc.), antifungal ingredients(imidazole-based antifungal agenst, such as clotrimazole, clotrimazoleacetate, miconazole acetate, econazole acetate, befornazole, oxiconazoleacetate, sulconazole acetate, neticonazole hydrochloride, befornazoleand tioconazole, omoconazole acetate, allylamine-based antifungalagents, such as terbinafine, terbinafine hydrochloride and naftifine,benzylamine-based antifungal agents such as butenafine, allylamine-basedantifungal agents such as amorphin hydrochloride, thiocarbamicacid-based antifungal agents such as tolnaftate, tolciclate,pyrrolnitrine, exalamide, cyclopirox olamine, etc.), tissue-repairingingredients (allantoin, heparin-like substances, vitamin A palmitate,vitamin D2, retinol acetate, retinol, vitamin A oil, panthenol, etc.),astringent ingredients (zinc oxide, Acanthopanax senticosus extract,aluminum chloride, yellow gourd extract, salts thereof, citric acid,white birch extract, tea extract, hop extract, horse chestnut extract,etc.), dead skin flexibilizer ingredients (urea, glycerin, concentratedglycerin, potassium hydroxide, salicylic acid, sulfur, colloidal sulfur,resorcin, glycolic acid, lactic acid, sodium sulfate, etc.),moisturizing ingredients (butylene glycol, pyrrolidone sodiumcarboxylate, propylene glycol, ribonucleic acid sodium, Angelica utilisextract, asparaginic acid, alanine, arginine, sodium alginate, althaeaextract, aloe vera extract, oyster-extract, hydrolyzed keratin,hydrolyzed collagen, hydrolyzed conchiolin, hydrolyzed egg shellmembrane, hydrolyzed albumen, hydrolyzed silk, brown algae extract,quince extract, bramble extract, xylitol, chitosan, cucumber extract,quince seed extract, glycine, glycerin, glucose, cape aloe extract,cystin, cysteine, mallow extract, serine, sorbitol, trehalose, sodiumlactate, sodium hyaluronate, placenta extract, sponge gourd extract,multi fee, mannitol, lily extract, lactoferrin, lysine, apple extract,royal jelly extract, etc.), emollient ingredients (almond oil, avocadooil, olive oil, oleic acid, orange roughy oil, cacao butter, carrotextract, squalane, ceramide, evening primrose oil, grape seed oil,jojoba oil, macadamia nut oil, mineral oil, mink oil, eucalyptus oil,rosehip oil, vaseline, etc.), whitening ingredients (ascorbic acid,ascorbic acid derivatives, arbutin, recinol, ellagic acid, glutathione,kojic acid, rose fruit extract, kiwi extract, etc.), ultravioletprotective ingredients (para-aminobenzoic acid, para-aminobenzoic acidethyl ester, para-aminobenzoic acid glycerin ester,para-dimethylaminobenzoic acid amyl alcohol ester,para-dimethylaminobenzoic acid 2-ethylhexyl alcohol ester,t-butylmethoxydibenzoyl methane, oxybenzones, octyl triazone, octylsalicylate, ethyl diisopropyl cinnamate, methyl diisopropyl cinnamate,cinoxate, dimethoxy cinnamic acid glyceryl octanate, octyl dimethoxybenzylidene dioxoimidazolidine propionate, Chinese tea extract,drometrizole, isopropyl para-methoxycinnamate, homosalate, octyl methoxycinnamate, etc.), herbal extract ingredients, vitamins, amino acids orminerals, without being limited thereto.

The film forming agent, the cosmetic composition or the cosmetic mayinclude other solvents, thinners or additives depending on applications.

Here, the solvent or thinner component may be exemplified depending onapplications of the composition, use forms, and the like, for example,by alcohols (e.g., polyethylene glycol, etc.), ethers (diethyl ether,etc.), glycol ethers (cellosolve species such as methyl cellosolve;dialkyleneglycol alkyl ethers such as diethylene glycol ethyl ether,etc.), nitriles (acetonitrile, etc.), ketones (acetone, etc.) or esters(carboxylic acid alkyl esters such as ethyl acetate, etc.).

In addition, the additive may be exemplified by not only plasticizer,wetting agents, antifoaming agents, coloring agents, preservatives,aromatics, flavors, pigments or thickeners but also common componentsused in quasi-drugs, pharmaceuticals or cosmetics, for example, powderybase materials or carriers (binders, disintegrants, excipients orlubricants and the like), oily base materials or carriers (animal andvegetable oils, waxes, vaseline, paraffin oils, silicone oils, higherfatty acid esters or higher fatty acids, etc.), aqueous base materialsor carriers (gel base materials, such as xanthan gum, etc.),preservatives, chelating agents, antioxidants, refreshing agents,stabilizers, fluidizers, emulsifiers, thickeners, buffering agents,dispersing agent, absorbents, moisturizing agents, wetting agents,desiccants, antistatic agents or other resins (polyamide-based resins,olefin-based resins such as hydrogenated polybutene, etc.), withoutbeing limited thereto.

The method for preparing the film forming agent, the cosmeticcomposition or the cosmetic using the above components or other knownadditional components, if necessary is not particularly limited, and aknown manner may be applied.

Advantageous Effects

The present application can provide a functional polymer, suitable forforming a film, showing a low solubility in polar and non-polar solventsand having low blurring characteristics against the solvents. Thepolymer of the present application may be applied to various uses, andfor example, when it is applied to cosmetics such as mascara, or othermedicinal uses, it may represent a resistance to various solvents, suchas sebum, sweat and tears, so that it may be used in a film formingagent, a cosmetic composition or a cosmetic capable of maintainingdurability such as makeup.

MODE FOR INVENTION

Hereinafter, the polymers of the present application and the like willbe specifically explained through Examples and Comparative Examples, butthe scope of the polymer is not limited to the following examples. InExamples and Comparative Examples below, each physical property wasevaluated by the following methods.

1. Solubility Measurement of Polymer

Polymer solutions prepared in Examples or Comparative Examples are keptat a temperature of about 150° C. for about 60 minutes to volatilize thesolvent. 1 g of the polymer volatilizing the solvent is collected. 1 gof the above collected polymer is added to 5 g of a solvent (hexane,ethyl acetate, acetone or water) and stirred at room temperature for 30minutes, and then the remaining polymer, which is un-dissolved, isremoved. The transparent solution with removing the remaining polymer issampled and dried at 150° C. for 30 minutes to remove the solvent.Through mass comparison of the remaining polymer in the solutionremoving the solvent the solid content is calculated. The concentrationof the polymer dissolved in the solvent is measured through the solidcontent and the solubility is obtained by converting the measured amountto a value for 100 g of the solvent. If the solution is not transparenteven after removing the remaining polymer, the solution is passedthrough a filter (0.45 μm NYLON) to obtain the transparent solution, andthen the above process is carried out.

<Solubility Evaluation Criteria>

A: when the solubility is 15 or more

B: when the solubility is more than 10 and less than 15

C: when the solubility is more than 5 and up to 10

D: when the solubility is up to 5

2. Molecular Weight Measurement

The weight average molecular weight (Mw) and molecular weightdistribution (PDI) were measured under the following conditions by usingGPC, and the measurement results were converted by using the standardpolystyrene of Agilent system in preparing a calibration curve.

<Measurement Conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U. S.)

Column: PL Mixed B two connected

Column temperature: 40° C.

Eluant: THF (Tetrahydrofuran)

Flow rate: 1.0 mL/min

Concentration: ˜1 mg/mL (100 μL injection)

3. Calculation of Glass Transition Temperature

The glass transition temperature (Tg) was calculated depending on themonomer composition by the following Equation.1/Tg=ΣWn/Tn  <Equation>

wherein Wn is a weight fraction of each monomer in the polymer, Tn is aglass transition temperature appearing when the monomer has formed ahomopolymer, and the right-hand side of the equation is a result ofsumming all the calculated values after calculating the value (Wn/Tn)obtained by dividing the weight fraction of the used monomer by theglass transition temperature appearing when the monomer has formed ahomopolymer for each monomer.

4. Sebum Blurring Test

Composition A is prepared by dissolving a polymer prepared in eachpreparation example in isododecane as a solvent in a concentration ofabout 10% by weight, and dissolving ceresine, a synthetic wax and amicrocrystalline wax in concentrations of 7% by weight, 6% by weight and8% by weight, respectively at a temperature of about 90° C.Subsequently, Composition B is prepared by adding propylene carbonateand disteardimonium hectorite to the Composition A in concentrations of8% by weight and 2% by weight, respectively and dispersing themuniformly for 20 minutes. Subsequently, iron oxide (CI 77499) is addedthereto in a concentration of 6% by weight and then an appropriateamount of preservatives is added, followed by being dispersed for 30minutes and then slowly cooled to about 28° C., to prepare a mascaraformulation.

Sebum blurring test using the prepared mascara formulation was dividedinto an in-vitro test and an in-vivo test and carried out, the detailsof which are as follows.

In-Vitro Test

The mascara formulation is applied on a slide glass (glass plate) to athickness of 30 μm and then completely dried at room temperature. Afterdrying, water and sebum are dropped on the mascara by 0.1 g,respectively, and after being left to stand for 20 minutes, a cotton padis placed thereon and reciprocated 30 times with a force of 200 gf, andthen the degrees of being smeared on the cotton pad are compared andevaluated in accordance with the following criteria.

<Evaluation Criteria>

When the degrees of being smeared on the cotton pad were compared on ascale within a range of 0 to 5, by setting the case of smearing nomascara at all on the cotton pad to 5 and setting the case of applyingthe polymer of the following comparative example 1 as a control group(reference) to 3, the superior level relative to the control group wasquantified to one decimal place as a relative comparison betweensamples.

In-Vivo Test:

Images are taken 6 hours after applying the prepared mascara formulationon eyelashes of a test subject, compared and evaluated according to thefollowing criteria.

<Evaluation Criteria>

After a lapse of 6 hours, images are taken and shown as values byimage-analyzing blurring areas. On image-analyzing, the area of blurringwas quantified as a pixel unit and shown.

5. Water Resistance Test

The above prepared mascara formulation is applied on a slide glass(glass plate) to a thickness of 30 μm and then completely dried at roomtemperature, and the dried sample is immersed in water at roomtemperature for about 30 minutes and then taken out to evaluate thewater resistance depending on the following criteria according to massdecrease rates (=100×(1−B/A), unit:%, wherein A is the total mass of theslide glass applying the mascara formulation and B is the total mass ofthe slide glass measured after immersing it in water, then taking outand removing moisture).

<Evaluation Criteria>

A: when the mass decrease rate is at least 5%

B: when the mass decrease rate exceeds 5%

Examples 1 to 3 and Comparative Examples 1 to 3

Monomers for preparing polymers were applied to types and proportionsshown in Table 1 below. As shown in Table 1 below, monomers are mixedand then introduced into isododecane as a solvent to have a monomerconcentration of 35% by weight, and an appropriate amount of a thermalinitiator (V-65, 2,2′-azobis(2,4-dimethyl valeronitrile) is introducedthereto and then the reactor is sealed. Subsequently, the dissolvedoxygen is removed by bubbling with nitrogen at room temperature forabout 30 minutes together with stirring and the nitrogen bubbling isfurther carried out for about 40 minutes while elevating the reactionmixture removing oxygen to a temperature of about 70° C. If thetemperature increases to 70° C. through the above process, thepolymerization reaction proceeds by the thermal initiator dissolved inthe solvent. After performing the reaction for about 24 hours, thereaction is completed by decreasing the temperature to room temperature(In Table below, TMSS of Comparative Example 3 corresponds to MQ-1600Resin from Dow Corning Co.).

TABLE 1 Example Comparative Example 1 2 3 1 2 3 Polymer A B C D E F LMA19 16 19 EHMA 29 30 IBOMA 69 60 69 60 71 EOEOEA 10 10 10 10 10 KBM-503 1KBE-503 2 5 TMSS 100 Content unit: g LMA: lauryl methacrylate(solubility parameter of a homopolymer: 8.2 (cal/cm³)^(1/2)) EHMA:ethylhexyl methacrylate (solubility parameter of a homopolymer: 8.3(cal/cm³)^(1/2)) IBOMA: isobornyl methacrylate (solubility parameter ofa homopolymer: 8.1 (cal/cm³)^(1/2)) EOEOEA: ethoxyethoxy ethylacrylate(solubility parameter of a homopolymer: 10.6 (cal/cm³)^(1/2)) KBE-503:3-methacyloxypropyl triethoxysilane KBM-503: 3-methacyloxypropyltrimethoxylsilane TMSS: trimethylsiloxysilicate (solubility parameter ofa homopolymer: 7.5 (cal/cm³)^(1/2)) (Trimethyl siloxysilicate: DowCorning MQ-1600 Resin)

1. NMR Evaluation Results

FIG. 1 is an NMR analysis result for the polymer of Example 1. As can beseen from the drawing, as a result of analyzing the polymer of Example1, 1H peaks derived from ═CH2 of the double bond terminus were littleidentified, whereby it could be seen that the polymerization has beencarried out effectively. In addition, —CH2- and —CH— peaks adjacent to—COO— of LMA, IBOMA and KBE-503 forming the polymer, and —OCH2CH2O—peaks of EOEOEA and peaks derived from SiO(CH2-)3 of KBE-503 wereidentified in the region of 4.7 pm to 3.3 ppm as an area value of 10.Peaks derived from —CH2- of the side chain and —CH3 derived from themeta-position were identified in the region of 2.0 ppm to 1.5 ppm as anarea value of 35, and 1H peaks from —CH2CH— or —CH2CH2- derived from thepolymer backbone were identified in 1.5 ppm to 0.5 ppm as an area valueof 55.

In the case of Example 2, as a result of NMR evaluation, 1H peaksderived from ═CH2 of the double bond terminus were also littleidentified. —CH— peaks adjacent to —COO— of EHMA, IBOMA and KBM-503forming the polymer, peaks derived from —OCH2CH2O— of EOEOEA and peaksderived from —Si—O(CH3)3 of KBM-503 were identified in the region of 5.0pm to 3.5 ppm as an area value of 9. In addition, from —CH2- of the sidechain and —CH3 derived from the meta-position, peaks having an areavalue of 36 were identified in the region of 2.5 ppm to 1.3 ppm, and 1Harea value identified from —CH2CH— or —CH2CH2-derived from the polymerbackbone was 55 in the region of 1.3 ppm to 0.5 ppm.

In the case of the polymer of Example 3, as a result of analyzing by theprocedure according to 1H-NMR evaluation method, 1H peaks derived from═CH2 of the double bond terminus were little identified. —CH2- and —CH—peaks adjacent to —COO— of LMA, IBOMA and KBE-503 forming the polymer,—OCH2CH2O— peaks of EOEOEA and peaks from —SiO(CH2-)3 of KBE-503 wereidentified in the region of 4.7 ppm to 3.3 ppm as an area value of 11.From —CH2- of the side chain and —CH3 derived from the meta-position,peaks having an area value of 35 were identified in the region of 2.0ppm to 1.5 ppm, and 1H area value identified from —CH2CH— and —CH2CH2-derived from the polymer backbone was 55 in 1.5 ppm to 0.5 ppm.

In the case of the polymer of Comparative Example 1, 1H peaks derivedfrom ═CH2 of the double bond terminus were also little observed, and—CH— peaks adjacent to —COO— of EHMA and IBOMA forming the polymer andpeaks derived from —OCH2CH2O— of EOEOEA were identified in the region of5.0 ppm to 3.5 ppm as an area value of 9. From —CH2- of the side chainand —CH3 derived from the meta-position, peaks having an area value of35 were identified in the region of 2.5 ppm to 1.3 ppm, and 1H areavalue identified from —CH2CH— and —CH2CH2- derived from the polymerbackbone was 56 in the region of 1.3 ppm to 0.5 ppm.

In the case of the polymer of Comparative Example 2, 1H peaks derivedfrom ═CH2 of the double bond terminus were also little identified, and—CH2- and —CH— peaks adjacent to —COO— of LMA and IBOMA forming thepolymer and peaks derived from —OCH2CH2O— of EOEOEA were identified inthe region of 4.7 ppm to 3.3 ppm as an area value of 10. In addition,from —CH2- of the side chain and —CH3 derived from the meta-position,peaks having an area value of 32 were identified in the region of 2.0ppm to 1.5 ppm, and 1H area value identified from —CH2CH— and —CH2CH2-derived from the polymer backbone was 58 in 1.5 ppm to 0.5 ppm.

2. Physical Property Evaluation

The results of measuring physical properties for each polymer ofExamples and Comparative Examples were summarized and described in Table2 below.

TABLE 2 Example Comparative Example 1 2 3 1 2 3 Polymer A B C D E FSolubility Hexane D D D D C A Ethyl acetate A A A A A A Acetone D D D CC A Water D D D D C C Weight average molecular 200,000 350,000 250,000340,000 200,000 weight Glass transition temperature 31 39 32 39 34 (°C.) Sebum blurring In-vitro 4.2 4.2 4.5 3.9 4.0 3.0 In-vivo 2000 21001700 3200 3100 4500 Water resistance test A A A A A A

It can be confirmed from the above results that in the case of thepolymer satisfying the requirements of the present application, itexhibits a low solubility in polar solvents (water, acetone) andnon-polar solvents (hexane) and exhibits an excellent solubility insolvents (ethyl acetate) having middle characteristics. Also, if such apolymer was applied, it was confirmed to have an excellent sebumresistance even in the sebum blurring test while securing waterresistance.

The invention claimed is:
 1. A film forming agent comprising: an activeingredient comprising medicinal ingredients, physiologically activeingredients, pharmacologically active ingredients or cosmeticingredients, and a polymer comprising polymerized units of a firstmonomer of which homopolymer has a solubility parameter of less than10.0 (cal/cm³)^(1/2); polymerized units of a second monomer of whichhomopolymer has a solubility parameter of 10.0 (cal/cm³)^(1/2) or more;and polymerized units of a compound of Formula 5 below:

wherein, R₁ to R₆ are each independently hydrogen, a hydroxy group, analkyl group, an alkoxy group, an alkenyl group, a (meth)acryloyl group,a (meth)acryloylalkyl group, a (meth)acryloyloxy group or a(meth)acryloyloxyalkyl group, provided that at least one is an alkenylgroup, a (meth)acryloyl group, a (meth)acryloylalkyl group, a(meth)acryloyloxy group or a (meth)acryloyloxyalkyl group, and n is anumber in a range of 0 to 20, wherein the first monomer is a compoundrepresented by Formula 1 below:

wherein, Q is an alkyl group, B is an alicyclic hydrocarbon group having6 to 12 carbon atoms, wherein the polymer comprises the polymerizedunits of the first monomer in an amount of at least 50% based on weight,wherein a glass transition temperature of the polymer is in a range of10° C. to 110° C., and wherein the polymer has a solubility of 10 orless at room temperature in a solvent having a dielectric constant (25°C.) in a range of 1 to 3, a solubility of 10 or less at room temperaturein a solvent having a dielectric constant (25° C.) in a range of 75 to85, and a solubility of 15 or more at room temperature in a solventhaving a dielectric constant (25° C.) in a range of 4 to 15, wherein thesecond monomer is a compound represented by Formula 2 or 3 below:

wherein Q is hydrogen or an alkyl group, U is an alkylene group, Z is analkyl group, and m is a number in a range of 1 to 100:

wherein Q is hydrogen or an alkyl group, A and U are each independentlyan alkylene group, X is a cyano group, and n is a number in a range of 1to
 100. 2. The film forming agent according to claim 1, wherein thehomompolymer of the first monomer has a solubility parameter in a rangeof 5 (cal/cm³)^(1/2) to 9.5 (cal/cm3)^(1/2).
 3. The film forming agentaccording to claim 1, wherein the homopolymer of the second monomer hasa solubility parameter in a range of 10.0 (cal/cm³)^(1/2) to 15.0(cal/cm3)^(1/2).
 4. The film forming agent according to claim 1, whereinin Formula 2 Q is hydrogen or an alkyl group having 1 to 4 carbon atoms,U is an alkylene group having 1 to 4 carbon atoms, Z is an alkyl grouphaving 1 to 4 carbon atoms and m is a number in a range of 1 to
 30. 5.The film forming agent according to claim 1, wherein in Formula 5 atleast one of R₁ to R₆ is an alkoxy group.
 6. The film formingagentaccording to claim 1, wherein in Formula 5 n is 0, R₁, R₃, R₅ andR₆ are each independently hydrogen, an alkyl group, an alkoxy group, a(meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group, providedthat at least one of R₁, R₃, R₅ and R₆ is an alkoxy group and at leastone of R₁, R₃, R₅ and R₆ is also a (meth)acryloylalkyl group or a(meth)acryloyloxyalkyl group.
 7. The film forming agent according toclaim 1, wherein in Formula 5 n is a number in a range of 1 to 20, R₁ toR₆ are each independently an alkyl group, a (meth)acryloylalkyl group ora (meth)acryloyloxyalkyl group, provided that at least one of R₁ to R₆is a (meth)acryloylalkyl group or a (meth)acryloyloxyalkyl group.
 8. Thefilm forming agent according to claim 1, wherein the polymer comprises 5to 15 parts by weight of the polymerized units of the second monomer and1 to 8 parts by weight of the polymerized units of the compound ofFormula 5 based on 100 parts by weight of the polymerized units of thefirst monomer.